Abstract
One Hundred Fifty-Seven nm photodissociation of singly protonated peptides generates unusual distributions of fragment ions. When the charge is localized at the C-terminus of the peptide, spectra are dominated by x-, v-, and w-type fragments. When it is sequestered at the N-terminus, a- and d-type ions are overwhelmingly abundant. Evidence is presented suggesting that the fragmentation occurs via photolytic radical cleavage of the peptide backbone at the bond between the α- and carbonyl-carbons followed by radical elimination to form the observed daughter ions.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Hunt, D. F.; Bone, W. M.; Shabanowitz, J.; Rhodes, J.; Ballard, J. M. Sequence analysis of oligopeptides by secondary ion/collision activated dissociation mass spectrometry. Anal. Chem. 1981, 53, 1704–1706.
Cantin, G. T.; Yates, J. R. III. Strategies for shotgun identification of post-translational modifications by mass spectrometry. J. Chromatogr. A 2004, 1053, 7–14.
Price, W. D.; Schnier, P. D.; Williams, E. R. Tandem mass spectrometry of large biomolecule ions by blackbody infrared radiative dissociation. Anal. Chem. 1996, 68, 859–866.
Zimmerman, J. A.; Watson, C. H.; Eyler, J. R. Multiphoton ionization of laser-desorbed neutral molecules in a Fourier transform ion cyclotron resonance mass spectrometer. Anal. Chem. 1991, 63, 361–365.
Bowers, W. D.; Delbert, S. S.; Hunter, R. L.; McIver, R. T., Jr. Fragmentation of oligopeptide ions using ultraviolet laser radiation and Fourier transform mass spectrometry. J. Am. Chem. Soc. 1984, 106, 7288–7289.
Martin, S. A.; Hill, J. A.; Kittrell, C.; Biemann, K. Photon-induced dissociation with a four-sector tandem mass spectrometer. J. Am. Soc. Mass Spectrom. 1990, 1, 107–109.
Barbacci, D. C.; Russell, D. H. Sequence and side-chain specific photofragment (193 nm) ions from protonated Substance P by matrix-assisted laser desorption ionization time-of-flight mass spectrometry. J. Am. Soc. Mass Spectrom. 1999, 10, 1038–1040.
Oh, J. Y.; Moon, J. H.; Kim, M. S. Tandem time-of-flight mass spectrometer for photodissociation of biopolymer ions generated by matrix-assisted laser desorption ionization (MALDI-TOF-PD-TOF) using a linear-plus-quadratic potential reflectron. J. Am. Soc. Mass Spectrom. 2004, 15, 1248–1259.
Thompson, M. S.; Cui, W.; Reilly, J. P. Fragmentation of singly-charged peptides by photodissociation at λ = 157 nm. Angew. Chem. Int. Ed 2004, 43, 4791–4794.
Williams, E. R.; Henry, K. D.; McLerty, F. W.; Shabanowitz, J.; Hunt, D. F. Surface-induced dissociation of peptide ions in Fourier-transform mass spectrometry. J. Am. Soc. Mass Spectrom. 1990, 1, 413–416.
Sleno, L.; Volmer, D. A. Ion activation methods for tandem mass spectrometry. J. Mass. Spectrom. 2004, 39, 1091–1112.
Wysocki, V. H.; Tsaprailis, G.; Smith, L. L.; Breci, L. A. Mobile and localized protons: A framework for understanding peptide dissociation. J. Mass Spectrom. 2000, 35, 1399–1406.
Roepstorff, P.; Fohlman, J. Proposal for a common nomenclature for sequence ions in mass spectra of peptides. Biomed. Mass Spectrom. 1984, 11, 601.
Johnson, R. S.; Martin, S. A.; Biemann, K. Collision-induced fragmentation of (M+H)+ ions of peptides. Side chain specific sequence ions. Int. J. Mass Spectrom. Ion Processes 1988, 86, 137–154.
Jensen, N. J.; Tomer, K. B.; Gross, M. L. Gas-phase ion decompositions occurring remote to a charge site. J. Am. Chem. Soc. 1985, 107, 1863–1868.
Gross, M. L. Charge-remote fragmentations: Method, mechanism, and applications. Int. J. Mass Spectrom. Ion Processes 1992, 118/119, 137–165.
Cheng, C.; Gross, M. L. Applications and mechanisms of charge-remote fragmentation. Mass Spectrom. Rev. 2000, 19, 398–420.
Summerfield, S. G.; Dale, V. C. M.; Despeyrous, D. D.; Jennings, K. R. Charge-remote losses of small neutrals from protonated and Group I metal-peptide complexes of peptides. Eur. J. Mass Spectrom. 1995, 1, 183–194.
Zaia, J.; Biemann, K. Comparison of charged derivatives for high energy collisional-induced dissociation tandem mass spectrometry. J. Am. Soc. Mass Spectrom. 1995, 6, 428.
Sadagopan, N.; Watson, J. T. Investigation of the tris(trimethoxyphenyl)phosphonium acetyl charged derivatives of peptides by electrospray ionization mass spectrometry and tandem mass spectrometry. J. Am. Soc. Mass Spectrom. 2000, 11, 107–119.
Huang, Z.-H.; Wu, J.; Roth, K. D. W.; Yang, Y.; Gage, D. A.; Watson, J. T. A. picomole-scale method for charge derivatization of peptides for sequence analysis by mass spectrometry. Anal. Chem. 1997, 69, 137–144.
Liao, P.-C.; Huang, Z.-H.; Allison, J. Charge remote fragmentation of peptides following attachment of a fixed positive charge: A matrix-assisted laser desorption/ionization postsource decay study. J. Am. Soc. Mass Spectrom. 1997, 8, 501–509.
Johnson, R. S.; Martin, S. A.; Biemann, K.; Stults, J. T.; Watson, J. T. Novel fragmentation processes of peptides by collision-induced decomposition in a tandem mass spectrometer: Differentiation of leucine and isoleucine. Anal. Chem. 1987, 59, 2621–2625.
Zubarev, R. A.; Kelleher, N. L.; McLerty, F. W. Electron capture dissociation of multiply charged protein cations. A nonergodic process. J. Am. Chem. Soc. 1998, 120, 3265–3266.
Syka, J. E. P.; Coon, J. J.; Schroeder, M. J.; Shabanowitz, J.; Hunt, D. F. Peptide and protein sequence analysis by electron transfer dissociation mass spectrometry. Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 9528–9533.
Zubarev, R. A.; Kruger, N. A.; Fridriksson, E. K.; Lewis, M. A.; Horn, D. M.; Carpenter, B. K.; McLerty, F. W. Electron capture dissociation of gaseous multiply-charged proteins is favored at disulfide bonds and other sites of high hydrogen atom inity. J. Am. Chem. Soc. 1999, 121, 2857–2862.
Breuker, K.; Oh, H.; Lin, C.; Carpenter, B. K.; McLerty, F. W. Nonergodic and conformational control of the electron capture dissociation of protein cations. Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 14011–14016.
Hu, Y.; Hadas, B.; Davidovitz, M.; Balta, B.; Lifshitz, C. Does IVR take place prior to peptide ion dissociation?. J. Phys. Chem. A 2003, 107, 6507–6514.
Thompson, M. S.; Cui, W.; Reilly, J. P. MALDI photodissociation TOF-TOF mass spectrometry. Proceedings of the 51st ASMS Conference on Mass Spectrometry and Allied Topics; Montreal, Quebec, June, 2003.
Williams, E. R.; Furlong, J. J. P.; McLerty, F. W. Efficiency of collisionally-activated dissociation and 193-nm photodissociation of peptide ions in Fourier transform mass spectrometry. J. Am. Soc. Mass Spectrom. 1990, 1, 289–294.
Oh, J. Y.; Moon, J. H.; Kim, M. S. Sequence- and site-specific photodissociation at 266 nm of protonated synthetic polypeptides containing a tryptophanyl residue. Rapid Commun. Mass Spectrom. 2004, 18, 2706–2712.
Robin, M. Higher excited states of polyatomic molecules, Vol. II; Academic Press: Orlando, FL, 1975, p. 139.
Peterson, D. L.; Simpson, W. T. Polarized electronic absorption spectrum of amides with assignments of transitions. J. Am. Chem. Soc. 1957, 79, 2375–2382.
Clark, L. B. Polarization assignments in the vacuum UV spectra of the primary amide, carboxyl, and peptide groups. J. Am. Chem. Soc. 1995, 117, 7974–7986.
Woody, R. W.; Koslowski, A. Recent developments in the electronic spectroscopy of amides and a-helical polypeptides. Biophys. Chem. 2002, 101/102, 535–551.
Suckau, D.; Resemann, A.; Schuerenberg, M.; Hufnagel, P.; Franzen, J.; Holle, A. A novel MALDI LIFT-TOF/TOF mass spectrometer for proteomics. Anal. Bioanal. Chem. 2003, 376, 952–965.
Medzihradszky, K. F.; Campbell, J. M.; Baldwin, M. A.; Falick, A. M.; Juhasz, P.; Vestal, M. L.; Burlingame, A. L. The characteristics of peptide collision-induced dissociation using a high-performance MALDI-TOF/TOF tandem mass spectrometer. Anal. Chem. 2000, 72, 552–558.
Christian, N. P.; Alexander, A. W.; Reilly, J. P. Design and evaluation of a low-cost, high-speed signal amplifier. Rev. Sci. Instrum. 2001, 72, 243–246.
Beardsley, R. L.; Reilly, J. P. Optimization of guanidination procedures for MALDI mass mapping. Anal. Chem. 2002, 74, 1884–1890.
Eng, J. K.; McCormack, A. L.; Yates, J. R. III. An approach to correlate tandem mass spectral data of peptides with amino acid sequences in a protein database. J. Am. Soc. Mass Spectrom. 1994, 5, 976–989.
Papayannopoulos, I. A. The interpretation of collision-induced dissociation tandem mass spectra of peptides. Mass Spectrom. Rev. 1995, 14, 49–73.
Meroueh, O.; Hase, W. L. Collisional activation of small peptides. J. Phys. Chem. A 1999, 103, 3981–3990.
Despeyroux, D.; Wright, A. D.; Jennings, K. R. Comparison of collision-induced dissociation and surface induced dissociation mass spectra of peptides obtained using a four-sector mass spectrometer. Int. J. Mass Spectrom. Ion Processes 1993, 126, 95–99.
Medzihradszky, K. F.; Adams, G. W.; Burlingame, A. L.; Bateman, R. H.; Green, M. R. Peptide sequence determination by matrix-assisted laser desorption ionization employing a tandem double focusing magnetic-orthogonal acceleration time-of-flight mass spectrometer. J. Am. Soc. Mass Spectrom. 1996, 7, 1–10.
Stimson, E.; Truong, O.; Richter, W. J.; Waterfield, M. D.; Burlingame, A. L. Enhancement of charge-remote fragmentation in protonated peptides by high-energy CID MALDI-TOF-MS using “cold” matrices. Int. J. Mass Spectrom. Ion Processes 1997, 169/170, 231–240.
Norrish, R. G. W.; Crone, H. G.; Saltmarsh, O. D. Primary photochemical reactions. Part V. The spectroscopy and photochemical decomposition of acetone. J. Chem. Soc. 1934, 1456–1464.
Turro, N. J. Modern molecular photochemistry; Benjamin/Cummings: Menlo Park, NJ, 1978, pp. 528–532.
Bosco, S. R.; Cirillo, A.; Timmons, R. B. Photolysis of formamides and acetamides studies by electron spin resonance. J. Am. Chem. Soc. 1969, 91, 3140–3143.
Spengler, B.; Kirsch, D.; Kaufmann, R. Metastable decay of peptides and proteins in matrix-assisted laser-desorption mass spectrometry. Rapid Commun. Mass Spectrom. 1991, 5, 198–202.
Spengler, B.; Kirsch, D.; Kaufmann, R. Fundamental aspects of postsource decay in matrix-assisted laser desorption mass spectrometry. 1. Residual gas effects. J. Phys. Chem. 1992, 96, 9678–9684.
Gluckmann, M.; Karas, M. Special feature: Perspective—The initial ion velocity and its dependence on matrix, analyte, and preparation method in ultraviolet matrix-assisted laser desorption ionization. J. Mass Spectrom. 1999, 34, 467–477.
Zenobi, R.; Knochenmuss, R. Ion formation in MALDI mass spectrometry. Mass Spectrom. Rev. 1998, 17, 337–366.
Luo, G. H.; Marginean, I.; Vertes, A. Internal energy of ions generated by matrix-assisted laser desorption/ionization. Anal. Chem 2002, 74, 6185–6190.
Hettick, J. M.; McCurdy, K. L.; Barbacci, D. C.; Russell, D. H. Optimization of sample preparation for peptide sequencing by MALDI-TOF photofragment mass spectrometry. Anal. Chem. 2001, 73, 5378–5386.
Koster, C.; Castoro, J. A.; Wilkins, C. L. High-resolution matrix-assisted laser desorption ionization of biomolecules by Fourier-transform mass-spectrometry. J. Am. Chem. Soc. 1992, 114, 7572–7574.
Shufang, N.; Wenzhu, Z.; Chait, B. T. Direct comparison of infrared and ultraviolet wavelength matrix-assisted laser desorption/ionization mass spectrometry of proteins. J. Am. Soc. Mass Spectrom. 1998, 9, 1–7.
Strupat, K.; Karas, M.; Hillenkamp, F. 2,5-Dihydroxybenzoic acid: A new matrix for laser desorption-ionization mass spectrometry. Int. J. Mass Spectrom. Ion Processes 1991, 111, 89–102.
Harrison, A. G. The gas-phase basicities and proton inities of amino acids and peptides. Mass Spectrom. Rev. 1997, 16, 201–217.
Dongre, A. R.; Jones, J. L.; Somogyi, A.; Wysocki, V. H. Influence of peptide composition, gas-phase basicity, and chemical modification on fragmentation efficiency: Evidence for the mobile proton model. J. Am. Chem. Soc. 1996, 118, 8365–8374.
Beardsley, R. L.; Karty, J. A.; Reilly, J. P. Enhancing the intensities of lysine-terminated tryptic peptide ions in matrix-assisted laser desorption/ionization mass spectrometry. Rapid Commun. Mass Spectrom. 2000, 14, 2147–2153.
Kim, S. K.; Pedersen, S.; Zewail, A. H. Direct femtosecond observation of the transient intermediate in the alpha-cleavage reaction of (CH3)2CO to 2CH3+CO: Resolving the issue of concertedness. J. Chem. Phys. 1995, 103, 477–480.
Diau, E. W.-G.; Herek, J. L.; Kim, Z. H.; Zewail, A. H. Femtosecond activation of reactions and the concept of nonergodic molecules. Science 1998, 279, 847–851.
Zubarev, R. A.; Horn, D. M.; Fridriksson, E. K.; Kelleher, N. L.; Kruger, N. A.; Lewis, M. A.; Carpenter, B. K.; McLerty, F. W. Electron capture dissociation for structural characterization of multiply charged protein cations. Anal. Chem. 2000, 72, 563–573.
Author information
Authors and Affiliations
Corresponding author
Additional information
Published online June 24, 2005
Rights and permissions
About this article
Cite this article
Cui, W., Thompson, M.S. & Reilly, J.P. Pathways of Peptide Ion Fragmentation Induced by Vacuum Ultraviolet Light. J Am Soc Mass Spectrom 16, 1384–1398 (2005). https://doi.org/10.1016/j.jasms.2005.03.050
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1016/j.jasms.2005.03.050